Compound of the benzanthrone-pyrazolanthrone series and a process of preparing it



Patented Jan. 16, 1934 UNITED STATES COMPOUND O F T H E BENZANTHRONE- PYRAZOLANTHRONE S E R I E S AND A PROCESS OF PREPARING IT Karl Wilke and Josef Stock, Frankfort-on-the- Main-Hochst, and Fritz Schubert, Frankforton-the-Main-Sindlingen, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing.

Application February 20, 1930,

Serial No. 430,120, and in Germany March 4,

16 Claims.

The present invention relates to new compounds of the benzanthrone-pyrazolanthrone series and a process of preparing the same.

We have found that new valuable vat dyestuffs are obtainable by subjecting to the action of an alkaline condensing agent a compound of the following general formula:

wherein X stands for hydrogen X1 stands for hydrogen X2 represents a polynuclear ring system, for instance, of an unsubstituted or a substituted anthraquinone or an anthraquinone derivative in a broad sense, for instance, of a benzanthrone, or

stands for a polynuclear heterocyclic ring system, for instance, of a pyrazolanthrone or a carbazole, N, X1 and X2 being members of the heterocyclic nucleus.

200 C. We prefer to use a temperature of about 100 C. and to prolong the reaction for about 5-9 hours.

The reaction is preferably carried out in the presence of an organic diluent with the addition 30 of an alkaline condensing agent.

The new dyestuffs obtainable by the above condensation process possess the following general properties: they are dark pastes of a blackish violet to dark green to greenish black coloration. The dry dyestuff powders are bluish violet, violet black or greenish black. The products dissolve in concentrated sulfuric acid with a coloration varying between wine red, brown, brownish violet, blackish violet, brownish olive, green, grey green 7 to greenish black. The vats are generally blue, in some cases grey or green. Cotton is dyed in these vats blue, grey or green shades. The fastness properties of the dyeings obtained are generally very good.

At the present time we could not yet definitely ascertain the constitutional formulae of our new products. It is obvious that between the pyrazolanthrone nucleus and the benzanthrone nucleus a further ring closure occurs with the'formation of benzanthrone-pyrazolanthrone that probably however, the dyestuff nucleus undergoes some further structural change during the condensation process inasmuch as the products obtainable according to our new process seem in many cases not to be identical with the products obtainable by reacting the corresponding amino compounds with a corresponding halogen substituted benzanthr one-pyrazolanthrone. From a chemical point of View it seems to be possible that at least in some cases a further formation of a carbazole or similar nucleus might occur according to the following probable formulae:

ii OVE {13H N N/ ui, H y i: I I l) i, I

' t g I O The reaction may be carried out at an elevated temperature, for instance, at about 90 C. to about wherein X1 stands for hydrogen 0 X2 represents a polynuclear ring system, for in- 0 stance, of an unsubstituted or a substituted anthraquinone or an anthraquinone derivative in a broad sense, for instance, or" a benzanthrone.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight, unless otherwise stated;

(1) 55 parts of pyrazolanthrone and 20 parts of finely subdivided potassium carbonate are stirred for 2 hours in 1300 parts by volume of nitrobenzene, the temperature of the oil bath being about 195 (3., whereby the red potassium salt of the pyrazolanthrone is formed, 95 parts of dibrominated benzanthrone are then introduced and the whole is heated to boiling for 4 hours while stirring. The mixture now contains monobromo 132- l -benzanthronyl Py l-pyrazolanthrone. It is allowed to cool for some time, a mixture of 56 parts of l-aminoanthraquinone, 56 parts of anhydrous sodium acetate and 20 parts of copper carbonate is then introduced and the whole is again heated to boiling for 16 hours. After cooling, the sparingly soluble condensation product separates in the form of brilliant chocolate-brown crystals. It is filtered and washed with nitrobenzene, alcohol and water. Any copper salt which may still be present is removed by extraction with boiling dilute hydrochloric acid whereafter the product is dried. The anthraquinonylamino Bz 1 benzanthronyl Pyl-pyrazolanthrone thus obtained dissolves in concentrated sulphuric acid to a brownish yellow solution from which reddish yellow flakes separate on dilution with water.

100 parts of the said anthraquinonylaminobenzanthronyl-pyrazolanthrone are melted, while stirring, with 500 parts of caustic potash and 400 parts of alcohol for about 7-8 hours at 95 C.100 C. The mixture is then poured on water and the dyestuff thus formed, which is partly obtained in a dissolved state as leuco compound, is separated completely by blowing air through the aqueous suspension. After the precipitate has been filtered and washed, a nearly black paste is obtained which in the dry state forms a black dyestuff powder. The product dissolves in concentrated sulfuric acid to a green solution from which bluish grey flakes separate on addition of water. The dyestuiii dyes cotton in a blue alkaline hydrosulfite vat greenish blue-grey shades of excellent properties of fastness.

The constitution of the dyestuii obtained according to this example is unknown. The new dyestufi yields greyish tints of a considerably more greenish hue than the dyestuff of Example 16 of the copending US. application Ser. No. 106,726 filed November 12, 1929, in the name of Karl Wilke, Josef Stock and Fritz Schubert.

(2) By substituting in Example 1 the same quantity of Z-amino-anthraquinone for the 1- amino-anthraquinone an isomeric anthraquinonylamino Bz 1 benzanthronyl Py pyrazolanthrone is obtained in the form of a brown powder. It dissolves in concentrated sulphuric acid to a reddish brown solution from which it separates in yellowish brown flakes on dilution with water.

By treating this new intermediate product with an alkaline condensing agent according to Example 1, a dyestufl is obtained which dissolves in concentrated sulfuric acid to a blackish violet solution from which it separates in greenish blue- I grey flakes on addition of water. It dyes cotton from a greenish-blue alkaline hydrosulfite vat clear blue-grey tints of a redder shade than that of the dyeing obtained with the dyestuff of Example 1.

(3) By substituting in Example 1, 30 parts of 1.e-diamino-anthraquinone for the l-aminoanthraquinone, a condensation product is obtained in the form of a brownish black powder which dissolves in concentrated sulfuric acid to a brownish violet solution. By melting the condensation product with caustic potash a dyestufi is obtained which dissolves in concentrated sulfuric acid to a greenish black solution and dyes cotton in a blue vat bluish grey tints.

(4) By using in Example 1, instead of the aininoanthraquinone, 85.5 parts of l-amino-- benzoylaminoanthraquinone a (benzoyl-aminoanthraquinonyl) amino-benzanthronyl-pyrazolanthrone is obtained in the form of a brownish black powder which dissolves in concentrated sulfuric acid to a brown solution. The dyestuif which is obtained by melting this intermediate product in alcoholic caustic potash at 100 C. is a dark green paste or a greenish black powder. It dissolves in concentrated sulfuric acid to a dark green solution from which it is precipitated, on dilution with water, in blue-green flakes. It dyes cotton in a blue-green vat a very greenish blue-grey.

By using 1amino-5-benzoylamino-anthraquinone an isometric dyestuff is obtained in the form of a violet black paste or a black powder which dissolves in concentrated sulfuric acid to a green solution. In a finely dispersed state the dyestuff has a violet blue color and dyes in a greenish blue vat reddish blue-grey tints.

(5) By substituting in Example 1, 62.5 parts of 1-amino-anthraquinone-2-aldehyde for the aminoanthraquinone there is obtained, by way of a dark brown intermediate product which dissolves in sulfuric acid to a yellowish-red solution, a black dyestuff powder. The latter dissolves in concentrated sulfuric acid to a brown solution from which greenish blue-grey flakes separate on addition of water. The dyestufi gives a blue alkaline hydrosulfite vat and dyes cotton in a weak solution a neutral grey tint and in a concentrated solution a neutral black tint.

When melting the product in caustic potash, there occurs the condensation to the benzanthrone-pyrazolanthrone.

(6) 55 parts of pyrazolanthrone, 97 parts of dibrominated benzanthrone and 61.2 parts of Bzl-aminobenzanthrone are either condensed and melted together as indicated in Example 1, or 55 parts of pyrazolanthrone and 93.5 parts of mono- 130 nitrated Bz-l-bromobenzanthrone are condensed, reduced to the amino-compound and again condensed with 77.3 parts of Bz-l-bromo-benzanthrone and melted with caustic potash and a1- cohol. In both cases there is obtained, by way of 135 a yellowish brown intermediate product which dissolves in sulfuric acid to a cherry red solution, a greenish-black dyestuff powder. The finished dyestuiT dissolves in concentrated sulfuric acid to a brownish violet solution from which 140 green flakes separate on dilution with water. The dyestuff dyes cotton in a blue alkaline hydrosulfite vat greenish blue-grey tints.

(7) There is stirred at boiling temperature for 12 hours a mixture of 261i parts of the condensa- 145 tion product obtained from equimolecular quantities of pyrazolanthrone and dibrominated benzanthrone, 23.2 parts of the reduced condensation product obtained from equimolecular quantities cf pyrazolcanthrone and mono-nitrated Bz- 150 l-bromobenzanthrone, 600 parts of nitrobenzene, 25 parts of anhydrous sodium acetate and 6 parts of copper carbonate. After cooling, the product which has separated is filtered, washed, extracted by means of boiling dilute hydrochloric acid and dried. It is a brownish yellow powder which dissolves in concentrated sulfuric acid to a yellowish red solution.

By melting the intermediate body thus formed in alcoholic caustic potash at about 100 0., as described in Example 1, a dyestuff is obtained which dissolves in sulfuric acid to a violet-brown solution from which blue fiakes separate on addition of water. The dyestuff gives a greenish blue vat which dyes cotton greenish blue-grey tints.

I (8) This example describes the condensation of 1 molecular proportion of dibromo-benzanthrone with 2 molecules of pyrazolanthrone and production of a dyestuff from the product. 55 parts of pyrazolanthrone are stirred for half-anhour at about 190 C. in 1300 parts of nitrobenzene in the presence of 35 parts of finely subdivided potassium carbonate and there is first obtained the potassium salt of the pyrazolanthrone. 48.? parts of dibromobenzanthrone are then introduced and the whole is stirred for further 6 hours at boiling temperature. After cooling, the condensation product thus obtained is filtered, washed with nitrobenzene, alcohol and water and dried. It is a yellowish brown powder which dissolves in concentrated sulfuric acid to a yellowish red solution.

By melting this intermediate product with caustic potash in the presence of alcohol at about 100 C. a dyestuff is obtained which, in a dry state, is a bluish violet powder. It dissolves in concentrated sulfuric acid to a wine-red solution from which brilliant greenish-blue flakes separate on dilution with water. It gives a greenish blue alkaline hydrosulfite vat which dyes cotton clear greenish blue tints.

(9) By substituting in Example 1 a mixture of 45 parts of carbazole, 20 parts of potassium carbonate and 4 parts of copper carbonate for the mixture of aminoanthraquinone, sodium acetate and copper carbonate used in the second phase of the reaction, a brilliant orange yellow intermediate product of high melting point is obtained which dissolves in concentrated sulfuric acid to a yellowish red solution. By melting it in caustic potash a dyestuff is obtained which dyes cotton in a green-blue vat fast blue-grey tints.

(10) 51 parts of 8-chl0ropyrazolanthrone (cf. Berichte der Deutschen Chemischen Gesellschaft, vol. 45, page 2247), 62 parts of BZ-lbromobenzanthrone and 15 parts of finely subdivided. potassium carbonate are first stirred togetherat boiling temperature in 1300 parts of nitrobenzene until no more sparingly soluble red salt of the pyrazolanthrone can be detected. A mixture of 45 parts of l-aminoanthraquinone, 45 parts of anhydroussodium acetate and 10 parts of copper carbonate .is then introduced and the whole is further heated to boiling for 25 hours while stirring. On cooling the Bz-l-benzanthronyl-Py-l (anthraquinonyl-l-amino- 8 pyrazolanthrone) separates. After thesolution has been worked up in the usualmanner a reddish yellow brown powder is obtained which dissolves in concentrated sulfuric acid to a not very intense brownish red solution. When the product is melted in caustic potash according to Example 1, it is transformed into a vat-dyestuff which dyes cotton in a greenish grey-blue vat intense greenish greyblue tints. The new product dissolves in sulfuric acid to a turbid wine-red solution from which blue-grey flakes separate on addition of water.

(11) When using in Example 10,5-chloropyrazolanthrone (cf. British specification No. 264,503 in the name of I. G. Farbenindustrie Aktiengesellschaft of Frankfort-on-the-Main, Germany, dated January 13, 1926) instead of the isomeride a. brownish yellow red Bz-l-benzanthronyl-Py-l- (anthraquinonyl-1-amino-5-pyrazolanthrone) is obtained which dissolves in concentrated sulfuric acid to a reddish brown-yellow solution and yields, when melted in caustic potash a dyestuff which dyes in a blue-grey vat grey-green tints. It dissolves in sulfuric acid to a grey-green solution from which olive green flakes separate on addition of Water.

(12) 4-chloropyrazolanthrone (obtained from 1.4-dichloroanthraquinone and hydrazine in pyridine; a yellowish brown crystalline powder melting at 301302 C. and dissolving in concentrated sulfuric acid to a reddish yellow solution with an orange fluorescence) yields, when worked up according to Example 10 a reddish yellow-brown Bz-l-benzanthronyl-Py 1 -(anthraquinonyl 1- aminol-pyrazolanthrone) which dissolves in sulfuric acid to reddish yellow-brown solution. The dyestuff which is obtained by melting the product in caustic potash gives a greyish violetblue vat which dyes cotton olive-green tints. It dissolves in sulfuric acid to a brownish olive solution from which olive-colored flakes separate on addition of water.

(13) When using in Example 10, 60 parts of 3-bromopyrazolanthrone (obtainable from 1.3- dibromoanthraquinone and hydrazine in a solution of pyridine; melting point 310 C.-311 C.) instead of the chlorine derivative there is obtained a dark red-brown Bz-l-benzanthronyl-Py-l- (anthraquinonyl -1-am-in-o 3 pryazolanthrone) and from this intermediate product a dyestuffs which dyes cotton in a blue-grey vat olive green tints. The dry dyestuff dissolves in sulfuric acid to anolive-green solution from which grey-green flakes separate on addition of water.

(14) When using in Example 1, 64 parts of 5- .chloropyrazolanthrone instead of the pyrazolanthrone and, furthermore, twice the quantity of l-amino-anthraquinone and sodium acetate there is obtained as intermediate product a bordeauxred dianthraquinonylamino-benzanthronyl-pyrazolanthrone and from the latter a dyestuff which dyes cotton in a grey vat olive grey tints and dissolves in sulfuric acid to a green solution.

When working up 8-chloropyrazolanthrone in the same way there is obtained a vat dyestufi dyeing grey tints.

(15) By condensing 23.5 parts (1 mol.) of 8- amino-pyrazolanthrone (of. U. S. patent specification No. 1,329,435) with 62 parts (2 mol.) of Bz-l-bromobenzanthrone there is obtained as intermediate product a red powder which yields, when melted in caustic potash a dyestufi dissolving in sulfuric acid to a brown red solution and dyeing in a green-blue vat greenish blue-grey tints.

(16) By benzanthronizing 1.4-dichloro-anthraquinone in known manner a 5.8-dichlorobenzanthrone is obtained melting at 157 C.158 C. and by brominating the latter product a Bz-l-bromo- 5.8-dichlorobenzanthrone is obtained melting at 225 C.-226 C. i

By condensing 18.9 parts of the said Bz-lbromo-5.8-dichlorobenzanthrone with '11 parts of cyclic nucleus with an alkaline condensing agent pyrazolanthrone and subsequently with 25 parts to a temperature of about 90 -200 C. of l-aminoanthraquinone according to Example 2. The process which comprises heating a 1, a dark brown halogen-free Bz-l-[di-(anthracompound of the following general formula: 5 quinonyl-l-amino)-5.8-benzanthronyl]-Py-1-py- V 80 razolanthrone is obtained which dissolves in concentrated sulfuric acid to a red brown solution. When this intermediate product is melted in caustic potash it condenses to a dyestuff which dissolves in concentrated sulfuric acid to a yellowl ish green solution and dyes cotton in a green vat V O greenish grey tints.

(17) By substituting in Example 1, 60 parts of 1 U 1.2 diamino anthraquinone for the l-amino- X anthraquinone, there is obtained as intermediate product a brownish black amino-anthraquinonyl amino benzanthronyl pyrazolanthrone which dissolves in concentrated sulfuric acid to l 00 a brown-red solution and yields a dyestuif which wherein X Stands f r hydrogen 20 dyes cotton in a greenish blue vat vivid blue-grey X1 Stands for hydrogen 95 Thfi dry dyestufi powder dissolves c0n- X2 represents a polynuclear ystem or centrated sulfuric acid to a blackish brown solution from which it separates in the form of bluish green flakes on addition of water.

(18) 15.5 parts of dichloro-benzanthronyl- 100 pyrazolantnrone (obtainable by causing chlorine to act for five hours at ordinary temperature upon Bz-l-benzanthronyl-Py-l-pyrazolanthrone in a solution of chlorosulfonic acid in the presence of iodine; a yellow brown powder, soluble in concentrated sulfuric acid to a carrnine red 1 'n r e he 1 solution, content of chlorine 14.9 per cent, calcu- 3 The procesb Wh ch p is S am g com lated for the entrance of 2 atoms of chlopound of the following general formula:

rine:l3.'7 per cent) are heated to boiling for 18 T hours with 18 parts of l-amino-anthraquinone, 30 parts of sodium acetate, 0.5 part of copper carbonate and a trace of copper powder in 300 parts of nitrobenzene, while stirring. After 0001- I ing, the solution is filtered, the precipitate CO 40 washed with nitrobenzene and extracted by 1 115 boiling glacial acetic acid. The product in a dry U represents a polynuclear heterocyclic ring system, N, X1 and X2 being members of the heteroc'yclic nucleus with an alkaline condensing agent in the presence of an inert organic diluent to a temperature of about 90 C.200 C.

state is a dark powder which dissolves in concentrated sulfuric acid to a wine-red solution. a; By melting this intermediate product for '7 hours 45 in alcoholic caustic potash at 160 'C.-170 C. L K

there is obtained a dyestuif which in a dry state is a black powder and dissolves in concentrated wherein X Stands for hydrogen sulfuric acid to a green solution. It gives a dull X1 t d for hydrogen green alkaline hydrosulfite vat which dyes cotton 7 X2 represents a polynuclear ring t m, or

50 grey tints. X1

We claim: 1. The process which comprises heating a compound of the following general formula: X2

7 v represents a polynuclear heterocyclic ring system, 55 N, X1 and X2 being members of the heterocyclic nucleus with caustic potash to a temperature of about 90 c.-200 c.

I 4. The process which comprises heating a com- I 00 pound of the following probable formula: 60 X1 NN '7 H i I 65 I CO X wherein X stands for hydrogen 7 N-N 1 X1 stands for hydrogen I 70 X2 represents a polynuclear ring system, or f; X2

X'- co represents a polynuclear heterocyclic ring syswherein X stands for hydrogen 7 tem, N, X1 and X2 being members of the hetero- 1 Stands for hydrogen alkaline condensing agent to a temperature of C.-200 C. a compound of the following gen X2 represents a polynuclear ring system, or

represents a polynuclear heterocyclic ring system, N, X1 and X2 being members of the heterocyclic nucleus with caustic potash in the presence of an inert organic diluent to a temperature of about 90 C.-200 C.

5. The process which comprises heating a compound of the following formula:

wherein X stands for hydrogen X1 stands for hydrogen X2 represents a polynuclear ring system, or

represents a polynuclear heterocyclic ring system, N, X1 and X2 being members of the heterocyclic v nucleus with caustic potash in the presence of ethyl alcohol to a temperature of about C.

6. The process which comprises heating a compound of the following probable formula:

with caustic potash in the presence of ethyl alcohol to a temperature of about 100 C.

7. The compounds substantially identical with those which are obtainable by heating with an oral formula:

wherein X stands for hydrogen X1 stands for hydrogen X2 represents a polynuclear ring system, or

lowing formula:

said product being a nearly black paste, in the dry state a black dyestuif powder, which dyes W cotton in a blue alkaline hydrosulfite Vat green- 145 ish blue-grey shades of excellent properties of fastness.

9. The compound substantially identical with that which is obtainable by heating with caustic potash in the presence of ethyl alcohol to a tem- 150 perature of about 100 C. a compound of the fol- 12. The process which comprises heating a lowing formula: compound of the following probable formula:

I .2 said product dyeing cotton from a greenish grey- U blue vat intense greenish grey-blue tints. I

10. The process which comprises heating a compound of the general formula:

with caustic potash in the presence of ethyl alcohol to a temperature of about 100 C.

13. The process which comprises heating a compound of the following probable formula:

X Y NH }|TN \o 5 wherein X stands for hydrogen and Y tepresents. an anthraqumonyl group with with caustic potash in the presence of ethyl a1- caustic potash 1n the presence of ethyl alcohol cohol to a temperature of about to a temperature 14. The compounds substantially identical with The process Whlch compnses heatmg those obtainable by heating with caustic potash '50; compound of the general formula: in the presence of ethyl alcohol to a temperature of about 100 C. a compound of the following general formula:

H \o NN -N\ X X Y 5 X X wherein X stands for hydrogen and wherein X stands for hydrogen and Y represents an anthraquinonyl group.

Y represents an alpha-anthraquinonyl group 15. The compounds substantially identical with with caustic potash in the presence or" ethyl alcothose obtainable by heating with caustic potash hol to a temperature of about 100 C. in the presence of ethyl alcohol to a temperature of about 100 C. a compound of the following atemperature of about 100 C.acompound of the general formula:

H I NN Y wherein X stands for hydrogen and Y represents an alpha-anthraquinonyl group. 16. The compound substantially identical with that obtainable by heating with caustic potash to following formula:

KARL WILKE. J OSEF STOCK. FRITZ SCHUBERT. 

